Adsorptive Cathodic Stripping Voltammetry Research Articles

How to overcome the difficulty in assaying Ni in biodiesel samples? Extraction induced by microemulsion breaking and square wave adsorptive stripping voltammetry could be the answer

Herein, a simple, green, and relatively inexpensive approach to determine nickel (Ni) in biodiesel samples by square wave adsorptive cathodic stripping voltammetry (SWAdCSV) is presented. A method based on the accumulation of Ni as Ni(II)-dimethylglyoxime (Ni(II)(HDMG)2) on the glassy carbon electrode was carried out in a solution containing the aqueous phase extract (APhEx) obtained from an extraction induced by microemulsion breaking (EIMB), which was achieved by adding a few microliters of ultrapure water to a microemulsion composed of biodiesel, n-propanol and a diluted HNO3 solution. The LOD and LOQ were 0.2 μg L−1 and 0.8 μg L−1, respectively, and the accuracy was evaluated by recovery assays of spiked samples and by analyzing a standard reference material. Results obtained from a comparative method (HR-CS GF AAS) were also used for this evaluation. The method was applied to biodiesel samples produced from different feedstocks. To the best of the authors knowledge, it is the first time that: 1) Ni in biodiesel is determined by a voltammetric method; 2) EIMB is applied to extract Ni from this matrix and 3) this type of sample preparation method is used with adsorptive stripping voltammetry.

Recommendations for best practice for iron speciation by competitive ligand exchange adsorptive cathodic stripping voltammetry with salicylaldoxime

The method of competitive ligand exchange followed by adsorptive cathodic stripping voltammetry (CLE-AdCSV) allows for the determination of dissolved iron (DFe) organic speciation parameters, i.e., ligand concentration (LFe) and conditional stability constant (log KFe′Lcond). Investigation of DFe organic speciation by CLE-AdCSV has been conducted in a wide range of marine systems, but aspects of its application pose challenges that have yet to be explicitly addressed. Here, we present a set of observations and recommendations to work toward establishing best practice for DFe organic speciation measurements using the added ligand salicylaldoxime (SA). We detail conditioning procedures to ensure a stable AdCSV signal and discuss the processes at play during conditioning. We also present step-by-step guidelines to simplify CLE-AdCSV data treatment and interpretation using the softwares ECDSoft and ProMCC and a custom spreadsheet. We validate our application and interpretation methodology with the model siderophore deferoxamine B (DFO-B) in a natural seawater sample. The reproducibility of our application and interpretation methodology was evaluated by running duplicate titrations on 19 samples, many of which had been refrozen prior to the duplicate analysis. Nevertheless, 50% of the duplicate analyses agreed within 10% of their relative standard deviation (RSD), and up to 80% within 25% RSD, for both LFe and log KFe′Lcond. Finally, we compared the sequential addition and equilibration of DFe and SA with overnight equilibration after simultaneous addition of DFe and SA on 24 samples. We found a rather good agreement between both procedures, with 60% of samples within 25% RSD for LFe (and 43% of samples for log KFe′Lcond), and it was not possible to predict differences in LFe or log KFe′Lcond based on the method applied, suggesting specific association/dissociation kinetics for different ligand assemblages. Further investigation of the equilibration kinetics against SA may be helpful as a potential way to distinguish natural ligand assemblages.

Development of an Electroanalytical Method for Ronidazole Determination in Environmental and Food Matrices Using Boron-Doped Diamond Electrode

A novel electroanalytical approach is presented for the determination of ronidazole in environmental and food matrices by applying a cathodically pretreated boron-doped diamond electrode and the square-wave adsorptive cathodic stripping voltammetry technique. From the studies of cyclic voltammetry to investigate the electroactivity of the ronidazole molecule, the occurrence of an irreversible cathodic process was verified, which was more efficiently detected using the cathodically pretreated boron-doped diamond electrode compared to the anodically pretreated electrode. Still on the electrochemical response of ronidazole, the effects of pH and scan rate were studied and, its apparent diffusion coefficient was determined by chronoamperometry (8.20 × 10−6 cm2 s−1). Under optimal experimental conditions, the analytical curve obtained for ronidazole was linear in two concentration ranges (12.70 to 63.40 µmol L−1 and 76.04 to 126.2 µmol L−1), with a limit of detection of 2.55 µmol L−1. For intra- and inter-day repeatabilities, relative standard deviations of only 2.7 and 3.5% were verified, which demonstrated the stable analytical response of the electrode. Recovery percentages ranging from 96 to 100% were achieved in the analysis of natural water and whole milk samples. Therefore, the proposed electroanalytical method shows satisfactory analytical performance towards ronidazole determination in varied matrice samples.

A simple, fast and inexpensive approach to quantify low concentrations of iron in biodiesel by voltammetry after extraction induced by microemulsion breaking.

An alternative approach to assay iron (Fe) in biodiesel by differential pulse adsorptive cathodic stripping voltammetry (DPAdCSV) is presented herein. The sample treatment involved a simple, rapid, but effective extraction of Fe from biodiesel into an aqueous phase after microemulsion (ME) breaking. Then, Fe was determined as the complex Fe(III)-PAN (1-(2-pyridylazo)-2-naphthol) on a glassy carbon electrode (GCE) in the presence of bismuth (Bi(III)). The extraction induced by microemulsion breaking (EIMB) was achieved by adding 0.80 mL of ultrapure water into a water-in-oil ME containing 7.00 mL biodiesel, 2.70 mL n-propanol and 0.30 mL of 0.25 mol L-1 HNO3 solution. No deliberate addition of surfactant was necessary to form and maintain the ME. The EIMB resulted in a 1.30 mL lower aqueous phase extract (APhEx) and an upper oily phase. DP voltammograms were recorded with a portable potentiostat, showing the potentiality of carrying out the determination out of a central laboratory. Another feature was the non-necessity of deaerating the solution to eliminate the dissolved O2. The limits of detection (LOD) and quantification (LOQ) were 1.7 μg L-1 (140 mg kg-1) and 5.5 μg L-1 (455 mg kg-1), respectively. The accuracy of the method was evaluated by recovery assays of spiked samples, by analyzing a standard reference material and by comparisons with high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS).

Probe –integrated electrochemical sensing platform for measuring trace levels of parathion pesticides residues in water using Au- nanoparticles anchored Nafion nano composite modified glassy carbon electrode

Nanomaterial represents a principal driver to the adoption of electrochemical sensors for pesticides residues in water. Thus, the current strategy reports facile and highly sensitive electrochemical probe for monitoring parathion residues in water. The probe was based upon the use of Au nanoparticles (AuNPs) functionalized Nafion nanocomposites modified glassy carbon electrode (Au NPs/Nafion/GCE). The surface morphology, effective surface area and electrocatalytic performance of the Au NPs/Nafion/GCE were recorded and assigned using a scanning electron microscopy (SEM), cyclic voltammetry (CV) and electronic spectra. A straightforward protocol based upon combination of Au NPs/Nafion/GCE and square wave- adsorptive cathodic stripping voltammetry at pH 7.0 was established for parathion detection. The probe displayed two linear responses between the catholic peak current (ip,c) at − 0.8 V versus parathion concentrations over the ranges from 1.07 × 10−6 - 1.07 × 10−5 and 1.99 × 10−9 - 9.0 × 10−7 M with limits of detection (LOD) and quantification (LOQ) of 6.06 × 10−10 M and 2.0 × 10−9 M, respectively. The probe exhibited excellent reproducibility, repeatability with RSD of ± 0.5% (n = 5) at 8.0 × 10−7 M parathion. The probe was applied for parathion detection in water and validated by HPLC. The experimental Student texp and Fexp values were less than the tabulated ttab (2.78) and Ftab (6.39) at 95% probability.

GC:BiFE As an Useful Tool for the Quantification of Health Harmful Organic Compounds in Artisanal Spiritus Beverages Via ADSV

The bismuth film electrode (BiFE) has been used for the last two decades to substitute mercury electrodes for organics and inorganic compounds electroanalysis in the ppm and ppb range. Various of these compounds are considered such as important pollutants and potentially toxic for the human health. The electrode specificity is based in the ability to form amalgams or strong interactions with the analyte under test. The present work show the application of BiFE for detection and quantification of acetaldehyde (by-product of alcoholic fermentation) in EtOH:H2O (1:1).The analysis is carried out using Cathodic Adsorptive Stripping Square Wave Voltammetry (CAdSSWV) to take advantage of the ability to form strong interactions and the sensitivity of this technique.Fig 1. CAdSSWV of formaldehyde 50 ppm in EtOH:H2O (1:1) in LiClO4 0.1 M with acetate buffer (pH=4.5) as supporting electrolyte in BiFE supporting in Glassy Carbon. Edep= 0.2 V tdep=60 s. Reference electrode = Ag/AgCl Auxiliar electrode = Tungsten wireReferencesHutton, E., Ogorevc, B., Hocevar, S., Weldon, F., Smyth, M., Wang, J., An introduction to bismuth film electrode for use in cathodic electrochemical detection, Electrochem. comm., 2001, 3, 707 – 711 DOI: 10.1016/S1388-2481(01)00240-5Constant, M. G. Van den Berg, Jacinto Gil S., The determination of platinum in sea water by adsorptive cathodic stripping voltammetry, Analytica Chim. Acta, 1988, 129 – 139 DOI: 10.1016/S0003-2670(00)83675-2 Figure 1

Dopamine / Artesunate loaded polyhydroxybutyrate-g-cellulose- magnetite zinc oxide core shell nanocomposites: Synergistic antimicrobial and anticancer efficacy

In this study, polyhydroxybutyrate-g-cellulose - Fe3O4/ZnO (PHB-g-cell- Fe3O4/ZnO) nanocomposites (NCs) was synthesized and used as a delivery system for Dopamine (DO) /Artesunate (ART) drugs. Different types of cells (Ccell, Scell, Pcell) grafted with PHB were designed and mixed with different contents of Fe3O4/ZnO. Physical and chemical features of PHB-g-cell-Fe3O4/ZnO NCs were detected by FTIR, XRD, dynamic light scattering, transmission electron microscopy, and scanning electron microscopy. ART/DO drugs were loaded into PHB-g-cell- Fe3O4/ZnO NCs by single emulsion technique. The rate of drugs release was studied at different pHs (5.4, 7.4). Owing to the overlap between the absorption bands of both drugs, differential pulse adsorptive cathodic stripping voltammetry (DP-AdCSV) was used for the estimation of ART. To study the mechanism of ART and DO release, zero-order, first order, Hixon Crowell, Higuchi and Korsmeyer-Peppas models were applied to the experiment results. The results showed that Ic50 of ART @PHB-g-Ccell-10% DO@ Fe3O4/ZnO, ART @PHB-g-Pcell-10% DO@ Fe3O4/ZnO and ART @PHB-g-Scell-10% DO@ Fe3O4/ZnO were 21.22, 12.3, and 18.11 μg/mL, respectively. The results revealed that ART @PHB-g-Pcell-10% DO@ Fe3O4/ZnO was more effective against HCT-116 than the carriers loaded by a single drug. The antimicrobial efficacy of the nano-loaded drugs was considerably improved compared with free drugs.

A new sustainable approach using a composite material based on dimethylglyoxime and graphite immobilized on a 3D printed support for selective nickel detection

In this work, the development of a low-cost electrochemical device (U$ 0.02 per electrode) from the immobilization of a composite material (CM) based on graphite powder, dimethylglyoxime (DMG) and nail polish, on a 3D printed acrylonitrile butadiene styrene (ABS) support was proposed for direct, sensitive and selective determination of Ni(II) by square-wave cathodic adsorptive stripping voltammetry (SWCAdSV) in a reduction potential of −1.15 V (vs Ag|AgCl|KCl(sat)). The CM was properly characterized by X-ray diffraction (XRD) and Raman spectroscopy, additionally, the electrode surface of the proposed device (3Ds-CM/DMG) was morphologically characterized through images obtained by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electrode was applied as a proof of concept for monitoring Ni(II) levels in spiked tap water and synthetic urine samples. Under optimal analysis conditions, the developed method showed a good linear working range with concentrations ranging from 5 to 100 µg L−1, detectability (limit of detection) of 1.693 µg L−1, and excellent precision with relative standard deviation (RSD) of 2.9%. The doped samples at three concentration levels presented recovery values from 93.8 to 103.1%, using as a sample preparation step a simple dilution in supporting electrolyte. Furthermore, the results were analytically validated by statistical comparison with results obtained by flame atomic absorption spectrometry (F AAS). Finally, the electrodes showed RSD of 6.1% for construction reproducibility, which allows inferring that the proposed electrode proves to be a promising analytical tool with wide applicability.

A new tool for the determination of humic substances in natural waters: Pulsed voltammetry approach

Humic substances (HS) in natural waters can be determined with a new, simple and sensitive method based on their influence on the background current in a differential pulse - adsorptive cathodic stripping voltammetry. The proposed method, termed PB-HS (pulsed background - humic substances) is discussed in detail, including its application in natural samples from the Krka River estuary. The method was additionally compared with absorbance measurements as well as with the typical electrochemical HS quantification in natural waters based on HS complexation with molybdenum (Mo). A good correlation between methods was observed, with PB-HS showing slightly better sensitivity to humic compounds than classical spectrophotometry. Higher HS concentrations measured with the Mo-method may be due to the enhanced hydrophobicity reached at pH 2 that is required by the method. Advantages of the proposed PB-HS method, compared to existing voltammetric methods for HS quantification, are that it does not require any reagent addition (except buffer) and that it can be used at the natural pH of water as well as in a wide salinity range, which is crucial for its application in estuarine waters.

Determination of Bioavailable Dissolved Fe(III) at Different Fractionation Sizes at Coastal Water by Adsorptive-Cathodic Stripping Voltammetry

Determination of Bioavailable Dissolved Fe(III) at Different Fractionation Sizes at Coastal Water by Adsorptive-Cathodic Stripping Voltammetry

Identifying potential sources of iron-binding ligands in coastal Antarctic environments and the wider Southern Ocean

The availability of iron (Fe) to marine microbial communities is enhanced through complexation by ligands. In Fe limited environments, measuring the distribution and identifying the likely sources of ligands is therefore central to understanding the drivers of marine productivity. Antarctic coastal marine environments support highly productive ecosystems and are influenced by numerous sources of ligands, the magnitude of which varies both spatially and seasonally. Using competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-AdCSV) with 2-(2-thiazolylazo)-p-cresol (TAC) as a competing artificial ligand, this study investigates Fe-binding ligands (FeL) across the continental shelf break in the Mertz Glacier Region, East Antarctica (64 - 67°S; 138 - 154°E) during austral summer of 2019. The average FeL concentration was 0.86 ± 0.5 nM Eq Fe, with strong conditional stability constants (Log KFeL) averaging 23.1 ± 1.0. The strongest binding ligands were observed in modified circumpolar deep water (CDW), thought to be linked to bacterial Fe remineralisation and potential siderophore release. High proportions of excess unbound ligands (L’) were observed in surface waters, as a result of phytoplankton Fe uptake in the mixed layer and euphotic zone. However, FeL and L’ concentrations were greater at depth, suggesting ligands were supplied with dissolved Fe from upwelled CDW and particle remineralisation in benthic nepheloid layers over the shelf. Recent sea-ice melt appeared to support bacterial production in areas where Fe and ligands were exhausted. This study is included within our newly compiled Southern Ocean Ligand (SOLt) Collection, a database of publicly available Fe-binding ligand surveys performed south of 50°S. A review of the SOLt Collection brings attention to the paucity of ligand data collected along the East Antarctic coast and the difficulties in pinpointing sources of Fe and ligands in coastal environments. Elucidating poorly understood ligand sources is essential to predicting future Fe availability for microbial populations under rapid environmental change.

Cyclic Voltammetric determination of an antidepressant drug (Duloxetine hydrochloride) by using glassy carbon electrodes in bulk form and human biological fluids

Duloxetine hydrochloride was measured by employing Differential Pulse Cathodic Adsorptive Stripping Voltammetry (DP-CAdSV) and Square Wave Cathodic Adsorptive Stripping Voltammetry at the glassy carbon electrode (GCE) in bulk form and human biological fluids. Duloxetine hydrochloride exhibited one distinct and well-defined cathodic peak in the potential range -0.80 to -0.85 V v/s Ag/AgCl/KCl reference electrode. Cyclic Voltammetry, DP-CAdSV and SW-CAdSV showed one reduction wave with peak potential -0.85 V at pH 7. The proposed method's excellent sensitivity was demonstrated by the obtained LOD of 2.233X10-8mol L-1and a LOQ of 7.445X10-8mol L-1bulk by applying DP-CAdSV). On the other hand, a LOD of 5.099X10-8mol L-1and a LOQ of 1.699X10-7mol L-1bulk Duloxetine hydrochloride were achieved by applying SW-CAdSV method. The described methods could be recommended for use in trace analysis, quality control and clinical laboratories.

Bismuth-Chitosan Nanocomposite Sensors for Trace Level Detection of Ni(II) and Co(II) in Water Samples

Trace minerals play an essential role in methane production via anaerobic digestion (AD). It is important to monitor Ni(II) and Co(II) concentrations and the Ni/Co concentration ratio for the rapid diagnosis of the ecological status or activity of methanogens in AD. Electrochemical detection of Ni(II) and Co(II) was investigated by coating the Bi-chitosan nanocomposite on a glassy carbon electrode (GCE) via the electrodeposition technique. A square-wave adsorptive cathodic stripping voltammetry technique (SWAdCSV) was applied and optimized when dimethylglyoxime (DMG) was used as the chelating agent for Ni(II) and Co(II) measurements. The SWAdCSV results showed that the current peaks for Co(II) detection are 6.1 times greater than the current peaks for Ni(II) measurements, probably due to the different affinity of DMG molecules between Ni(II) and Co(II). DMG molecules demonstrated higher selectivity toward Co(II) cations compared to Ni(II). The modified Bi-chitosan GCE developed in this study showed a relatively wide range of the Ni(II) and Co(II) concentrations (2–100 µg L−1) with a limit of detection of 3.6 µg L−1 for Ni(II) and 2.4 µg L−1 for Co(II), respectively. The developed sensor was applied to Ni(II) and Co(II) spiked natural water samples and showed good performance of detection with 12 consecutive measurements. Overall, the fabricated sensor showed excellent sensitivity toward Ni(II) and Co(II) in natural water samples.

Simultaneous Adsorptive Stripping Voltammetric Analysis of Heavy Metals at Graphenated Cupferron Pencil Rods

Electroanalysis of heavy metal ions in the presence of cupferron ligands has been extensively studied due to its ability to form stable metallic coordination complexes. Herein, electrochemically reduced graphene oxide (ERGO) sheets were for the first time employed in conjunction with low-cost, disposable pencil graphite rods and in situ plated thin mercury films (HgF) for the simultaneous detection of Cd2+, Cu2+, Pb2+, and Zn2+ in the presence of cupferron as a chelating agent by square-wave adsorptive cathodic stripping voltammetry (SW-AdCSV). The technique is based on the catalytic reduction of adsorbed cupferron-metal ion complexes at the surface of the ERGO-HgF-PGE at 0.1 V for 60 s in 0.1 M acetate buffer solution (pH 4.6). Owing to the improved electronic and surface effects associated with ERGO inclusion, improved sensitivity was further achieved. Under optimized conditions, the ERGO-HgF-PGE showed a linear relationship from 20 to 200 μg.l−1 with detection limits below the US-EPA of 0.17 μg.l−1, 0.02 μg.l−1, 0.17 μg.l−1 and 0.14 μg.l−1 for Cd2+, Cu2+, Pb2+ and Zn2+, respectively at a deposition time of 60 s. The ERGO-HgF-PGE exhibited highly reproducible results with negligible intermetallic interferences and applied successfully to the determination of trace metals in tap water with satisfactory results.

Spectrophotometric Determination of Fe(II) and Fe(III) Using 5-(4-Ethylphenyl azo ) 2-Hydroxybenzaldehyde Oxime Reagent

Spectrophotometric Determination of Fe(II) and Fe(III) Using 5-(4-Ethylphenyl azo ) 2-Hydroxybenzaldehyde Oxime Reagent

Effect of salinity and temperature on the determination of dissolved iron-binding organic ligands in the polar marine environment

It is widely accepted that iron (Fe)-binding organic ligands play a crucial role in Fe distribution in the marine environment and thus in Fe biogeochemistry. Although Competitive Ligand Equilibration – Adsorptive Cathodic Stripping Voltammetry (CLE-AdCSV) is a well-established technique to investigate Fe chemical speciation in marine samples, several impediments still need to be addressed. These include the extrapolation of laboratory measurements to in-situ conditions, the harmonization of the analytical procedures used, and the applicability of the methods over salinity ranges wider than seawater (e.g., sea ice). This work focusses on the calibration of 2-(2-thiazolylazo)-p-cresol (TAC), salicylaldoxime (SA) and 1-nitroso-2-naphthol (NN), along the salinity range 1–90, and titration of natural samples at two different temperatures (4 °C and 20 °C). The artificial ligand concentration was 10 μM for TAC and 5 μM for SA and NN. Calibrations showed that increasing salinity caused a decrease in the conditional stability constants (logK'Fe’AL) for NN and SA (although different behaviours were noted for the two species FeSA and FeSA2). Less accuracy was noted using TAC, which behaved inconsistently outside the 21 < S < 35 range, and its use is therefore discouraged in fresh and highly saline waters. Titrations of natural samples showed that only SA covered the salinity range selected, up to 78, and its use is therefore recommended in sea-ice studies. The side reaction coefficient (logα'Fe’AL) of each artificial ligand was found to be influenced by temperature differently: logα'Fe’SA was higher at lower temperature (4 °C), whereas logα'Fe’SA2 and logα'Fe’NN3 increased with increasing temperature (to 20 °C). Although titrations performed at 4 °C highlighted that the uncomplexed Fe fraction was 14% lower than at 20 °C, with potential consequences on primary productivity, the percentage of natural Fe complexed was >99%. Future investigations should consider the analysis of the samples at a temperature as close as possible to in-situ conditions to reduce the potential temperature effects.

Equilibrium calculations of iron speciation and apparent iron solubility in the Celtic Sea at ambient seawater pH using the NICA-Donnan model

We used a combined ion pairing - organic matter speciation model (NICA-Donnan) to predict the organic complexation of iron (Fe) at ambient pH and temperature in the Celtic Sea. We optimized our model by direct comparison with Fe speciation determined by Adsorptive Cathodic Stripping Voltammetry using the added Fe-binding ligand 1-nitroso-2-naphthol (HNN) in the presence and absence of natural organic matter. We compared determined Fe speciation with simulated titrations obtained via application of the NICA-Donnan model with four different NICA parameter sets representing a range of binding site strengths and heterogeneities. We tested the assumption that binding sites scale to dissolved organic carbon (DOC) concentrations in marine waters. We found that a constant low DOC concentration resulted in an improved fit of our titration data to the simulated titrations, suggesting that inputs of autochthonous marine DOM may not increase the heterogeneity or concentrations of Fe binding sites. Using the optimal parameter set, we calculated pFe(III)´ (−log(∑Fe(OH)i3−i)) and apparent Fe(III) solubility (SFe(III)app) at ambient pH and temperature in the water column of the Celtic Sea. SFe(III)app was defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM formed at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH)3(s)). SFe(III)app was within range of the determined dissolved Fe concentrations observed after winter mixing on the shelf and in waters >1500 m depth at our most offshore stations. Our study supports the hypothesis that the ocean dissolved Fe inventory is controlled by the interplay between Fe solubility and Fe binding by organic matter, although the overall number of metal binding sites in the marine environment may not be directly scalable to DOC concentrations.

Distribution and size fractionation of nickel and cobalt species along the Amazon estuary and mixing plume

The Amazon River has the largest drainage basin in the world, making it a major source of trace elements and dissolved organic matter (DOM) to the Atlantic Ocean. However, despite the increasing anthropogenic impacts to the Amazon basin, few recent studies exist quantifying trace element data in this region. The aim of the study was to analyze the input and removal processes that influence the transport of Ni and Co species in the Amazon and Pará River estuaries and mixing zone. Toward this goal, this work provides a comprehensive mixing and speciation study for the trace elements Ni and Co. Samples were collected during a period of high river discharge on the RV Meteor cruise M147 (Amazon – GEOTRACES process study GApr11) in the Amazon and Pará River outflow regions, as well as the aging mixing plume to the north, a mangrove belt to the southeast and the North Brazil Current (NBC) seawater endmember. Here we present the results for labile particulate (>0.2 μm), labile and total dissolved (<0.2 μm), large colloidal (0.015–0.2 μm), soluble (<0.015 μm) and ultrafiltered (<1 and < 10 kDa) fractions of Ni and Co in surface waters (towed-fish) and along the water column at different depths (CTD) using comparative approaches by adsorptive cathodic stripping voltammetry (AdCSV) and inductively coupled plasma-mass spectrometry (ICP-MS). We observed good agreement between AdCSV and ICP-MS measurements for Ni, and to a lesser extent Co. In general, dissolved and soluble Ni and Co decreased with increasing salinity, however additional non-conservative removal was also observed and attributed to possible biological uptake and colloidal flocculation. Shipboard AdCSV measurements showed that dissolved Ni was present mostly in the “reactive” form as weak complexes, suggesting high bioavailability, while reactive dissolved Co was absent, indicating the presence of strong organic Co complexes. In both Ni and Co, an elevated colloidal fraction was observed at low salinity, suggesting removal of dissolved Ni and Co via colloidal flocculation upon seawater mixing, while the soluble species were transported to the Atlantic Ocean. At depth, the soluble phase dominated, and we observed concentration maxima at 500–1000 m, indicating the presence of Antarctic Intermediate Water (AIW) and possible biological regeneration. We also observed unique source signatures in dissolved and labile particulate Ni and Co species from the Amazon and Pará River outflow regions, in addition to a contribution from mangrove belt-associated groundwater.

Organic complexation of iron by strong ligands and siderophores in the eastern tropical North Pacific oxygen deficient zone

Continental margins are an important external source of dissolved iron to the marine environment. However, the mechanisms responsible for the offshore transport of dissolved iron is impacted by the resulting iron speciation. We characterized the iron speciation in the Eastern Tropical North Pacific (ETNP) oxygen deficient zone (ODZ), including dissolved iron, organic iron-binding ligands, and reduced iron. Organic iron-binding ligands were measured using both competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-ACSV) and liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) in order to explore the impact of organic ligands on dissolved iron (dFeT) and iron(II) biogeochemistry in the region. Organic ligands were present in high concentrations (1.06–5.30 nmol L−1) and exceeded dissolved iron concentrations (0.36–4.52 nmol L−1) at all locations. Iron-binding strengths (logKFeL,Fe′cond) ranged 11.22 to 12.75 and were elevated in the ODZ layer relative to the oxygenated water column. LC-ESI-MS revealed the presence of siderophores, or bacterially-produced organic ligands with high Fe-affinity, in all samples analyzed, suggesting these compounds may be produced by microbes in the ODZ despite high ambient dFeT concentrations. This study is the first to characterize siderophores in an ODZ environment to date, and the three siderophores found (amphibactin B, synechobactin c9, synechobactin c10) could contribute to the observed elevated logKFeL,Fe′cond of ligands in the ODZ. Comparative analysis of organic ligand logKFeL,Fe′cond values in other low oxygen environments suggests that strong ligands, including siderophores, could be present in other low oxygen regions. In a simple model of the shelf-to-offshore iron transport mechanism, strong organic iron-binding ligands had a large impact on the longevity and transport of iron in the ODZ. These results suggest that organic ligand composition can have an impact on iron distributions in the ETNP ODZ and regulate the offshore transport of iron to the open ocean.

Fe-binding organic ligands in coastal and frontal regions of the western Antarctic Peninsula

Abstract. Organic ligands are a key factor determining the availability of dissolved iron (DFe) in the high-nutrient low-chlorophyll (HNLC) areas of the Southern Ocean. In this study, organic speciation of Fe is investigated along a natural gradient of the western Antarctic Peninsula, from an ice-covered shelf to the open ocean. An electrochemical approach, competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV), was applied. Our results indicated that organic ligands in the surface water on the shelf are associated with ice-algal exudates, possibly combined with melting of sea ice. Organic ligands in the deeper shelf water are supplied via the resuspension of slope or shelf sediments. Further offshore, organic ligands are most likely related to the development of phytoplankton blooms in open ocean waters. On the shelf, total ligand concentrations ([Lt]) were between 1.2 and 6.4 nM eq. Fe. The organic ligands offshore ranged between 1.0 and 3.0 nM eq. Fe. The southern boundary of the Antarctic Circumpolar Current (SB ACC) separated the organic ligands on the shelf from bloom-associated ligands offshore. Overall, organic ligand concentrations always exceeded DFe concentrations (excess ligand concentration, [L′] = 0.8–5.0 nM eq. Fe). The [L′] made up to 80 % of [Lt], suggesting that any additional Fe input can be stabilized in the dissolved form via organic complexation. The denser modified Circumpolar Deep Water (mCDW) on the shelf showed the highest complexation capacity of Fe (αFe'L; the product of [L′] and conditional binding strength of ligands, KFe'Lcond). Since Fe is also supplied by shelf sediments and glacial discharge, the high complexation capacity over the shelf can keep Fe dissolved and available for local primary productivity later in the season upon sea-ice melting.